New dyestuffs and process for dyeing therewith



United States Patent-O NEW DYESTUFFS AND PROCESS FOR DYEING THEREWITHRobert Norman Heslop, Norman Legg, Jack Frankland Mawson, William ElliotStephen, and James Wardleworth, ail of Manchester, England, assignors toImperial Chemical Industries Limited, London, England, a corporation ofGreat Britain No Drawing. Application August 26, 1957 Serial No. 680,398

Claims priority, application Great Britain September 4, 1956 11 Claims.(Cl. 260-154) The invention relates to new dyestuffs and a process fordyeing therewith and more especially it relates to new dyestulfscontaining halogeno-pyrimidine rings and the process for colouringcellulosic textile materials therewith.

It has previously been proposed to manufacture dyestuffs by causing toreact together pyrimidine compounds containing reactive halogen atomsand aminoazo or aminoanthraquinone compounds but no dyestufls havehitherto been described which contain di-halogenopyrimidine radicals.

It has now been found that water-soluble dyestuffs may be obtained bythe interaction of equimolecular proportions of2:4:6-trihalogenopyrimidines and water-soluble coloured compounds whichcontain an amino group with at least one hydrogen atom attached to thenitrogen atom, and the water-soluble dyestuffs so obtained when appliedin conjunction with a treatment with an acid-binding agent to cellulosictextile materials give colourations which have better fastness to wettreatments than those obtained from previously described water-solubledyestufis contain- -ing pyrimidine rings applied in the same manner.

According to the invention there are provided as new dyestuffs the2:6-dihalogeno-4-pyrimidylaminoor the 4:6-dihalogeno-2-pyrimidylaminoderivatives of water-soluble colouredcompounds.

The new dyestuifs may be obtained by the interaction of at least onemolecular proportion of 2:4z-6-trihalogenopyrimidines with one molecularproportion of Watersoluble coloured compounds containing at least onemono-substituted or unsubstituted amino group and isolating thedihalogeno-pyrimidyl derivatives of the watersoluble compounds.

Suitable 2:4:6-trihalogenopyrimidines include, for example,2:4:6-trichloropyrimidine and 2:4:6-tribromopyrimidine. p

The water-soluble coloured compound may be a member of any of the knowndyestuff series, for example the azo, anthraquinone, phthalocyanine ornitro series, containing one or more amino groups of the type definedabove, and one or more ionogenic solubilising groups such as sulphonicacid or carboxylic acid groups.

The coloured compounds of the azo series containing amino groups whichmay be used as starting materials in the above process may be obtainedby a variety of methods. One method is to diazotise and aromatic primaryamine and couple the diazonium compound so obtained with a couplingcomponent containing an amino or monosubstituted amino group which afterthe coupling operation remains free to react, either the aromaticprimary amine, or the coupling component, or both, containing at leastone ionogenic solubilising group. Suitable aromatic primary amines whichmay be used in this manner to obmand p-chloroanilines,2:5-dichloroaniline, ccand ,8-

2,935,506 Patented May 3, 1960 ice 2 naphthylamine, 2:5-dimethylaniline,5-nitro-2-aminoanisole, 4-aminodiphenyl, aniline-2-, 3- and 4-carboxylicacids, Z-aminodiphenylether, 2-3- or. 4-aminobenzene sulphonamide orsulphonmonomethylor ethyl-amides or sulphon-di-methylor ethyl-amides,dihydrothio-p-toluidine monosulphonic acid or dihydrothio-p-toluidinedisulphonic acid, aniline-2-, -3- and -4-sulphonic acids, aniline2:5-disulphonic acid, 2:4-dimethylaniline-6-sulphonic acid, 3-aminobenzotrifluoride 4 sulphonic acid, 4 chloro 5-methylaniline-Z-sulphonic acid, 5-chloro-4-methylaniline- 2-sulphonicacid, 3-acetylamino-aniline-6-sulphonic acid,4-acetylamino-aniline-2-sulphonic acid, 4-chloroaniline- 2-sulphonicacid, 3:4-dichloroaniline-6-sulphonic acid, 4- methylaniline-Z-sulphonicacid, 3-methylaniline-6-sulphonic acid, 2:4-dimethoxyaniline-6-sulphonicacid, 4-' methoxyaniline-Z-sulphonic acid and S-methoxyaniline-Z-sulphonic acid, 2:S-dichloroaniline-4-sulphonic acid, 2-naphthylamine-4:8- and 6:8-disulphonic acids, l-naphthylamine-2-, 4-,5-, 6- or 7-monosulphonic acid, l-naphthylamine-3:6-disulphonic acid,2-naphthylamine 3:6- and 5:7-disulphonic acids and2-naphthylamine-3:6:8-t1'isulphonic acid, mand p-nitroaniline,4-nitro-aniline-2-sulphonic acid and 3-nitroaniline-6-sulphonic acid,mor paminoacetanilide, 4-amino-2-acetylaminotoluene 5 sulphonic acid.

Suitable coupling components include for example, 2- aminoandZ-methylamino-5-naphthol-7-sulphonic acids, 2-amino andZ-methylamino-8-naphthol-6-sulpohnic acids, l-aminoand1-ethylamino-S-naphthol-G-sulphonic acids and the corresponding 3:6- and4:6-disulphonic acids, 1-, 3'- or 4"-nninobenzoylamino-8-naphthol-3:6-and 4:6-disulphonic acids, aniline, oand m-anisidines, oand mtoluidines,2:5-dimethylaniline, 3-amino-4-methoxytoluene, 2:5-dimethoxyaniline,N-methylaniline, N-e'thyl-otoluidine, N-methyl-m-anisidine,3-methylamino-4-methoxytoluene, 1-(3-aminophenyl)-3-methyl-, carboxy,and carboethoxy-S-pyrazolones, l-(4'-aminophenyl)-3-methyl-, carboxy-,and carboethoxy-S-pyrazolones and 1-(4'- amino-3 '-carboxyphenyl) -3-methyl-5 -pyrazolone.

The aminoazo compounds which are to be interacted with thetrihalogeno-pyrimidine are not restricted to compounds containing onlyone azo group. Suitable disazo compounds which may be used may beobtained for example by tetrazotisation of an aromatic diaminecontaining two primary amino groups and coupling the tetrazo compound soobtained with 2 molecular proportions of one of the above-definedcoupling components or with 1 molecular proportion of each of two of theabove-defined coupling components or with one molecular proportion ofone of the above-defined coupling components and with one molecularproportion of a coupling component not containing an amino group, itbeing understood that the aromatic diamine or the coupling component (orat least one of the coupling components when two different couplingcomponents are used) contains at least one ionogenic solubilising group.Suitable aromatic diamines include, for example: benzidine,3:3-dimethoxybenzidine, benzidine-Z:2'-disulphonic acid, benzidine-3:3'-dicarboxylic acid, benzidine-3:3'-diglycollic acid and 44'-diaminostilbene-2 2-disulphonic acid.

Alternatively suitable disazo or polyazo compounds may be obtained bythe use of primary aromatic amines or diamines containing azo groups inthe above-described processes. As examples of suitable primary aromaticamines or diamines containing azo groups which may be used there may bementioned 4-aminoazobenzene-4-sulphonic acid,4'-amino-2-methylphenylazo-Z-naphthalene- 4:8-disulpl1onic acid and4-arnino-3-methoxy-2-methyl-4- nitro-2'-sulphoazobenzene.

A similar method of obtaining the coloured compounds of the azo serieswhich may be used as starting materials comprises coupling a couplingcomponent which optionally contains an amino or mono-substituted aminogroup with a diazonium compound which contains an amino ormono-substituted amino group, either the coupling component or thediazonium compound, or both containing at least one ionogenicsolubilising group. Such diazonium compounds may be obtained by methodsknown from the art, by the diazotisation of aromatic primary aminescontaining a second amino group or containing a mono-substituted aminogroup. Suitable aromatic primary amines include, for example p-phenylenediamine, 1:4-phenylenediamine-2sulphonic acid,1:4-phenylenediamine-Z-carboxylic acid and 1:4-diaminonaphtha1ene-2-sulphonic acid. As examples of coupling components which may be used inthis manner, there may be mentioned the coupling components listed aboveand also fi-naphthol, 2-naphthol-6- or 7-sulphonic acid, 2-naphthol-3:6- or 6:8 disulphonic acids, 1-naphthol-4-sulphonic acid,lphenyl-3methyl-S-pyrazolone, 1-4'-sulphophenyl- 3-methyl-5-pyrazolone,1- (2 '-dichloro-4-sulphophenyl) -3-methyl-5-p-yrazolone,2-benzoylamino5-naphthol-7- sulphonic acid, 1-benzylamino 8-naphthol-3z6or 4:6-disulphonic acid, phenol, p-cresol, acetoacetam'lide andacetoacet-2-methoxyanilide-S-sulphonic acid.

A further method of obtaining the coloured compounds of the azo serieswhich may be used as starting materials is to treat an azo or polyazocompound containing at least one ionogenic solubilising group and alsocontaining at least one acylamino group with aqueous acid or aqueousalkali in order to cause hydrolysis of the acylamino group or groups.Suitable azo or polyazo compounds may be obtained from aromatic primaryamines and/or coupling components containing acylamino groups. Suitablearomatic primary amines in addition to the acylaminoarylamines mentionedabove include, for example, monoacetylbenzidine,4-amino-1acetylaminonaphthalene-6sulphonic acid,4-arnino-4'-acetylaminodiphenyl-3sulphonic acid, 4 amino 4'acetylamino-stilbene-Z:2'-disulphonic acid, and suitable couplingcomponents include, for example 2-acetylarnino-5-naphthol-7-sulphonicacid, 2-acetylmethylamino 5 naphthol 7 sulphonic acid, 2 acetylaminoandacetylmethylamino-8-naphthol-6-sulphonic acids andlacetylamino-8-naphthol-3:6- and 4:6-disulphonic acids.

Yet a further method of obtaining the coloured compounds of the azoseries which may be used as starting materials is to treat an azo orpolyazo compound conring, with a reducing agent for example sodiumsulphide,

sodium hydrogen sulphide or sodium dior polysulphides, known to becapable of reducing an aromatic nitro compound to the correspondingamino compound.

Suitable coloured compounds of the anthraquinone series which may beused as starting materials for making the new dyestufr' of the inventionare those containing an amino group or a mono-substituted amino group assubstituents in an alkylamino or an arylamino group attached to analpha-position of the anthraquinone nucleus and also containing at leastone ionogenic solubilising group. As examples there may be mentionedl-amino- 4- (4'-aminoanilino-) anthraquinone 2:3-disulphonic acid andthe corresponding 2:3'z5- and 2:326-trisulphonic acids,l-amino-4-(4"-amino-4'-benzoylaminoaniline)anthraquinone-Z:3-disulphonicacid and the corresponding 2 3' 5 trisulphonic acid, 1-arnino-4- [4-(4"-aminophenylazo-)anilino-] anthraquinone-2:2-5-trisulphonic acid, 1-amino-4- (4'-amino-3 -carboxyanilino-) anthraquinone-2 :5- disulphonicacid, 1-amino-4-(3'-aminoanilino)anthraquinone-2:4'z5-trisulphonic acidand the corresponding 2:4- disulphonic acid,1-amino-4-[4-(4"-aminophenyl-)anilino-1anthraquinone-2:3":5-trisulphonicacid, 1-amino-4- (4' methylamino)anilino anthraquinone 2:3 disulphonicacid and the corresponding 2:3't5-trisulphonic acid,1-arnino-4-(4'-n-buty1amino) aniline-anthraquinone- 2:3'-disulphonicacid, 1-amino-4-(4'-methylamino-3'-carboxyanilino-)-2-sulphonic acid and1-amino-4-(3-betahydroxyethylarnino-)anilinoanthraquinone 2:5disulphonic acid, 14'-aminoanilinoanthraquinone-Z:3'-disulphonic acidand 1-amino-4-(4-amino-2-methoxyanilino) anthraquinone-2 3 '-disulphonicacid.

These starting materials of the anthraquinone series may themselves beobtained from anthraquinone compounds, containing a halogen atom or anitro group attached to the appropriate alpha-position of theanthraquinone nucleus, or from the leuco derivative of a 1:4- dihydroxy,diaminoor aminohydroxy-anthraquinone, by interacting the appropriateanthraquinone compound with at least one molecular proportion of analiphatic or an aromatic diamine, so choosing the starting materialsthat the ionogenic solubilising group is present in the anthraquinonecompound and/or the aliphatic or aromatic diamine. Alternatively anamino anthraquinone compound, optionally carrying one or more ionicsolubilising groups may be treated with a sulphonating agent, forexample sulphuric acid, chlorosulphuric acid, or oleum, in order tointroduce one or more sulphonic acid groups.

Coloured compounds of the phthalocyanine series which may be used asstarting materials for making the new dyestuifs of the invention arethose containing at least one ionogenic solubilising group and at leastone amino, or mono-substituted amino group. The amino ormono-substituted amino group or groups may be attached directly to thebenz-rings of the phthalocyanine nucleus or they may be attached theretothrough a divalent bridging radical for example, -phenylene-,--COphenylene-, SO -phenylene-, NH-phenylene-, --S-phenylene-,O-phenylene-, CH S-phenylene-, CH O-phenylene-, CH -phenylene-, SCH-phenyI- ene, -SO CH -phenylene-, SO NR-phenylene-CH -SO NR arylene NRCOphenylene, NRSOQ phenylene-, SO 0-phenylene-, CH CH NR- phenylene, -CHNH.CO-phenylene-, -4O NR-alkylene-, CH NR alkylene-, CONR-phenylene-CHmay be substituted, for example by halogen, alkyl and alkoxy.

As examples of aromatic divalent bridging radicals denoted by arylenethere may be mentioned aromatic nuclei, for example a benzene nucleus, anaphthalene nucleus, an acridine nucleus and a carbazole nucleus, whichnuclei may bear further substituents, and radicals of the formula:

wherein the benzene rings may bear further substituents and where D-stands for a bridging group, for example CH=CH-, NH-, -S-, -O, 40 -NO=N,N=N, NH.CO.NH-, CO.NH- --O.CH CH O and As specific examples of colouredcompounds of the phthalocyanine series which may be used in the processof the invention there may be mentioned copper phthalocyanine4-N-(4-amino-3-sulphophenyl-)sulphonamide- 4'.4":4"'-trisulphonic acid,cobalt phthalocyanine-4:4'- di-N-(3-amino-4'-sulphophenyl-)carbonamide-4:4"(-

dicarboxylic acid and copper-4-(4'-amino-3'-sulphoben and copperphthalocyanine di-[N-(4-amino-3-sulphophenyl-)sulphonamide] disulphonicacid.

The aminophthalocyanines used which contain a sulphonic acid can bemanufactured either by the sulphonation of known phthalocyaninescontaining primary or secondary amino groups or by synthesis frommixtures of phthalic acid derivatives and sulphonated phthalic acidderivatives. Thus treatment with a sulphonating agent for example oleumsuch as a 20% solution of sulphur trioxide in sulphuric acid of theamines described in United Kingdom specifications Nos. 569,200 and589,118 gives suitable aminophthalocyanines. The aminophthalocyaninecompounds so obtained are those containing the divalent bridgingradicals -phenylene-, --COphenylene-, SO -phenylene-, --NH-phenylene-,-S pheny1ene-, --O-phenylene, -CH S-pheny1ene-, -CH O-phenylene,

-CH -phenylene-, SCH -phenyleneand SO CH phenylene. 1

Those aminophthalocyanine compounds which contain the divalent bridgingradicals mentioned in the last paragraph and also those containing--NRCO-phenylene-, --SO NR-phenylene-, -NRSO -phenylene-, and S0 0-phenylene linkages as bridging radicals may be obtained by heatingtogether suitable derivatives of sulphonated phthalic acid and thesubstituted phthalic acids mentioned in the aforesaid United Kingdomspecifications Nos. 569,200 and 589,118 by the general methods known tobe used for the manufacture of phthalocyanines from suitable phthalicacid derivatives, for example, by heating together a mixture of4-sulphophthalic anhydride and 4-p-nitrobenzoylphthalic anhydride, urea,cupric chloride, and ammonium molybdate in o-dichlorobenzene at about150 0.; those which contain the --CH linkage may be obtained bysulphonation of the primary and secondary amines of United KingdomspecificationsNos. 717,137 and 724,212; those which contain the -CH NR-phenylenelinkage may be obtained by reacting a primary (or secondaryN-alkyl or cycloalkyl-)nitroaniline with a phthalocyanine containingchloromethyl and sulphonic or carboxylic acid groups obtained bychloromethylation of a phthalocyanine sulphonic or carboxylic acid, andreducing the product so obtained for example with sodium sulphide or byreacting a chloro-methyl phthalocyanine with for example adiaminobenzenesulphonic acid or carboxylic acid; those which contain theSO NR- alkylenelinkage may be obtained by reacting a phthalocyaninecontaining chlorosulphonyl groups with a mono acetyl alkylene diamine inthe presence of water, and treating the product so obtained (whichcontains both sulphonamide and sulphonic acid groups) with aqueousalkali to hydrolyse the acetylamino group; those which contain the -SONR-phenylene-CH linkage may be obtained in a similar manner by using anamino-N-benzylacetamide in place of the monoacety-alkylene diamine;those which contain the -CH .NR-alkylenelinkage may be obtained byreacting a phthalocyanine containing chloromethyl and sulphonic orcarboxylic acid groups with a monoacetyl alkylene diamine and treatingthe product so obtained with aqueous alkali to hydrolyse theacetyla-mino groups; those containing a direct link, so that the aminogroup is attached directly to the phthalocyanine nucleus, may beobtained by sulphonating the amino-phthalocyanines described in UnitedKingdom specification No. 529,847 or where a starting materialcontaining less than 4 amino groups attached to the phthalocyaninenucleus is desired, it may be obtained by heating together a mixture ofsuitable carboxyor sulphophthalic acid derivatives with one of thesubstituted phthalic acid derivatives used as staiting materials inUnited Kingdom specification No. 529,847 under conditions known to beused for the manufacture of phthalocyanines fromphthalic acidderivatives, for example by heating the :anhydrides with urea and acatalyst for example ammonium molybdate in an organic solvent, forexample o-dichlorobenzene, and reducing the nitrophthalicyaninesulphonic or carboxylic acid or hydrolysing the acylaminophthalocyaninesulphonic or oarboxylic acid so obtained by known methods for theconversion of aromatic nitro or acylamino compounds to the correspondingamines; and those containing the --CO.NR- phenylenelinkage may beobtained by reacting a phthalocyanine compound containing carboxylicacid chloride groups with a diaminobenzene sulphonic acid or carboxylicacid or withan aminobenzene sulphonic acid or an aminobenzoic acid whichalso contains a nitro group and reducing the nitro compound so obtained;and those containing the --CO--NR-phenylene-CH linkage may be obtainedby reacting a phthalocyanine compound con- I taining carboxylic acidchloride groups with an N-(aminobenzyl-) acetamide and subsequentlyhydrolysing. the product so obtained with aqueous alkali.

Suitable coloured compounds of the nitro series which may be used asstarting materials for making the new.

dyestulfs of the invention are those of the formula:

X Nor-D-u I-R where D stands for a naphthalene or benzene nucleus whichmay be further substituted wherein the nitrogen j atom N is in' theortho position to the nitro group, X stands for hydrogen or for ahydrocarbon radical which may be substituted, R stands for hydrogen orfor an organic radical attached to the nitrogen through a carbon atom,and wherein R may be connected to X when X is a hydrocarbon radical orto D, in the ortho position to the nitrogen atom N, to form aheterocyclic ring, which contains at least one amino or mono-substitutedamino group and which also contains at least one ionogenic solubilisinggroup.

As specific examples of coloured compounds of the nitro series which maybe used there may be mentioned sulphonic acid derivatives of substituteddiphenylamines and phenylnaphthylamines, for example 2:4-dinitro-4-aminodiphenylamine-3'-sulphonic acid, 2-nitro-3-amino-4-carboxydiphenylamine-4-sulphonic acid, 2-nitro -4'-(paminoanilino-)diphenylamine 3':4 disulphonic acid, 2- nitro 4methylarninodiphenylamine 3'14 disulphonic acid,2-nitro-4-methylamino-4-sulphon-beta-hydroxyethylamidodiphenylamine-3-sulphonicacid, 2-nitro-4-methylamino 4 carboxydiphenylamine-3'-sulphonic acid, 2-nitro-4-amino-l -naphthylphenylamine-4 6' disulphonic acid and 1 :5-dinitro-2: 6-di-(4-amino-3-sulphoanilino naphthalene. These sulphonicacid derivatives may conveniently be obtained by the reaction of theappropriately substituted o-nitrochloro-benzene or -naphthalene with theappropriately substituted diamine (at least one of the reagentscontaining a sulphonic acid group), in aqueous or alcoholic media in thepresence of an acid binding agent for example calcium carbonate atelevated temperatures for example at a temperature of C.

In the process for making the new dyestuflf of the invention, thereactants are dissolved or suspended in a liquid medium, preferably anaqueous medium, and the mixture is stirred until the reaction iscomplete. It is preferable to add an acid binding agent for examplesodium carbonate to the reaction mixture to remove the halogen acidformed during the reaction.

During the manufacture of the new dyestuffs it is generally preferableto carry out the reaction at a tempera ture above 50 C. and to isolatethe new dyestufis from the media in which they have been formed at a pHof from 6 to 8, and to dry the resultant dyestufi pastes, preferably inthe presence of buffering agents suitable for maintaining a pH value ofabout 6.5. Examples of such buflering agentsare mixtures of sodiumdihydrogen phos phate and disodium. hydrogen phosphate or of disodiumhydrogen phosphate and potassium dihydrogen' phosp ate.

Those new dyestulfs' of the invention which contain one or'more azogroups may be obtained by an alternative process by coupling a diazoniumcompound with a coupling component. wherein either the diazoniumcompound or the coupling component, or both, contains at least'oneionogenic solubilising group and either the diazonium compound or thecoupling component, or both, contains at least one 2:6-dihalogeno-4-pyrimidinylaminoor. at least one 4:6dihalogeho-Z-pyrimidinylaminogroup.

Suitable. coupling components containing these substltuents may beobtained from the coupling components containing an amino or.mono'substituted amino group by interaction with. a2:4:6-trihalogenopyrimidine using conditions similar to those describedabove for the process for makingthe new d'yestufis ofithe invention.

Suitable .diazonium compounds containing these substituents may beobtainedfrom aromatic primary amines containing a second primary aminogroup by interaction with a 2:4:6 trihalogenopyrimidine using conditionssimilar to those described above for'the process for making.

the new dyestufis of the invention.

In carrying out this alternative process, the coupling is preferablycarried out ata temperature below 5 C., conveniently at a temperaturebetween C. and C., andat as low a pH as is consistent with efficientcoupling in'order that side reactions, for example hydrolysis ofthe-halogen atoms remaining attached to the pyrimidine ring, areminimised- The new dyestuffs. of the invention may be used to coloursilk, wool, regenerated protein and cellulosic textile materials forexample cotton, linen and viscose rayon, by treating the textilematerial with an aqueous solution (which may be. a thickened printingpaste) of the dyestulfin conjunction with a treatment with anacid-binding agent, for example sodium hydroxide, potassium phosphate orsodium carbonate. The treatment with the acidbinding agent maybecarriedout prior to, simultaneously with or after the treatment withthe dyestulf.

When the acid-binding agent is applied simultaneously with the dyestufl,it may conveniently be dissolved in the dyestufi solution vor theprinting paste containing the dyestufi.

The dyestuff solution whether acid-binding agent is present or not, maycontain commonly used dyebath adjuvantsfor example sodium chloride,sodium sulphate, sodium alginate, urea and water-soluble alkyl ethers ofcellulose.

The printing paste, whether acid binding agent is present or not, maycontain commonly used adjuvants for example urea, and thickening agentsfor example methyl cellulose, starch and locust bean gum, but analginate, for. example sodium alginate is preferred as thickening agent.

Dyeing in the presence of acid binding agent is preferably carried outat elevated temperatures, for example at temperatures between 70 C. andthe boiling point of the dyestuff solution in order to improve theexhaustion and fixation of the dyestulf.

The textile material printed with printing paste containing acid-bindingagent is preferably steamed or heated inorder to fix the dyestulf on thetextile material.

When the acid-binding agent is applied in a separate step before orafter the dyestuif, it is preferably applied by treating the textilematerial with an aqueous solution of. the acid-binding agent, forexample by a padding technique. The aqueous solutions of acid-bindingagents thus used may also contain dyebath adjuvants of the kindmentioned 'above.

Both the solution of acid-binding agent and the dyestutf solutioncontaining the dyestufl? may be applied at room temperature or at. anelevated temperature, the textile material being optionally driedbetween the two treatments; but" when dyeing'protein' or regeneratedpro' tein fibres in conjunction with an acid-binding agent it ispreferred to use a temperature-below 50 C. It is preferred to heat orsteam cellulosic textile materials at an elevated temperature; forexample at C. or at a higher temperature for a short period of timeafter application of dyestuff and acid-binding agent to fix the dyestulfon the textile material.

The above processes may be modified by using, in place of-theacid-binding agent, a substance which on heating or steaming generatesan acid-binding agent, and thereafter subjecting the textile material toheat or steam after the treatment with the dyestutf and the saidsubstance, in order to generate the acid-binding agent.

As an example of a substance which on heating or steaming generates anacid-binding agent, there may be mentioned an alkali metal bicarbonate,for example sodium bicarbonate which on heating or steaming yieldssodium carbonate, and also sodium trichloroacetate which on steaminggenerates sodium carbonate.

The fastness to washing or subsequent wet processing of tohecolourations produced by the process of our' invention is in generalimproved by a scouring treatment in for example a hot aqueous solutionof soap and sodium'carbonate, followed by rinsing in hot water prior todrying.

The new dyestufis" may also be applied to silk, wool,. regeneratedprotein, polyamide and modified polyacrylo-' Example 1 23.25 parts ofthe disodium salt of the monoazo dyestuff obtained by coupling onemolecular proportion of diazotised 2-naphthylamine-4:8-disulphonic acidwith one molecular proportion of m-toluidine, are dissolved in 300 partsof water at 40 C. and the solution is'added to a solution of 9.1 partsof 2:4:6-trichloropyrirnidine in parts of ethanol. The mixture is heatedto 60 C. and stirred for 2% hours during which time a solution of 2.8parts of sodium carbonate in 25 parts of water is gradually added. Themixture is cooled to 15 C. and 25 parts of sodium chloride are added.The mixture is then filtered and the residue on the filter is washedwith 100 parts of 10% brine solution and dried at room temperature. Thedried product is then mixed with 2.0 parts of disodium hydrogenphosphate and 3.6 parts of potassium dihydrogen phosphate.

One molecular proportion of the dyestufi so obtained whentreated withhot alcoholic sodium hydroxide solution liberates two atomic equivalentsof chloride ion.

Example 2 24.05 parts of the disodium salt of the monoazo dyestufiobtained by coupling one molecular proportion of diazotised4-amino-toluene-3-sulphonie acid with one molecular proportion of2-amino-5-naphthol-7-sulphonic acid in alkaline solution are dissolvedin 400 parts of Water at 50 C. and the solution is added to 9.1 parts of2:4:6-trichloropyrimidine dissolved in 40 parts of acetone. The mixtureis heated to 60 C. and is stirred for 5 hours while a solution of 2.8parts of sodium carbonate in 25 parts of water is gradually added. Themixture is cooled to 15 C. and 60 parts of sodium chloride are added.The precipitated dyestuff is filtered off and dried at room temperature,and the dried product isthen mixed Example 3 14.6 parts of2-nitro-4'-aminodiphenylamine-3':4-disulphonic acid, 7.1 parts of2:4:6trichlorpyrimidine, 150 parts of water and 120 parts of ethylalcohol are stirred at the boil under a reflux condenser for 16 hours.The mixture is diluted to 1000 parts with water, then aqueous sodiumcarbonate solution is added to raise the pH of the solution to 6.4(about 40 parts of 2 N solution being required). 200 parts of salt arethen added and the solution is set aside for several days to awaitcrystallisation of. the product. When crystallisation is complete theproduct is filtered off, washed with 20% aqueous brine and dried at roomtemperature. A yellow dyestufi is obtained.

Example 4 In place of the 4-amino-2'-nitrodiphenylamine-3:4- disulphonicacid used in Example 3 there is used 17.8 parts of 2-nitro-4'-methylamino-4-sulphon-beta-hydroxyethylamidodiphenylamine 3'sulphonic acid. A similar product is obtained.

Example 5 100 parts of a bleached cotton fabric are padded through a 2%aqueous solution of the dyestuff of Example l at 50 C. and squeezedbetween rollers so that the weight is increased to 200 parts. The fabricis then dried in a hot flue and padded through an aqueous solutioncontaining 1% of sodium hydroxide which has been saturated with sodiumchloride at room temperature. It is immediately steamed at 100 C. for 1minute. The fabric is then washed in hot water, rinsed in a 0.5% aqueoussolution of sodium bicarbonate, treated in boiling 0.2% aqueous soapsolution for 5 minutes, rinsed in water and dried.

The fabric is coloured bright yellow and is fast to washing and tolight.

If the solution of dyestuif used in the above example is replaced by a1% aqueous solution of the dyestufi of Example 2, the fabric is colouredbright orange and has excellent fastness to washing and to light.

Example 6 90 parts of sodium chloride and 1 part of the dyestulf ofExample 1 are dissolved in 3,000 parts of water and 100 parts of viscoserayon yarn are added. The solution is heated to 90 C., and maintained atthis temperature for 30 minutes. 300 parts of a aqueous solution ofsodium carbonate are then added, and the dyeing is continued for 1 hour.The yarn is then rinsed in cold water, treated for 5 minutes at 95 C. ina 0.3% aqueous solution of a synthetic detergent, rinsed again in coldwater and dried. The yarn is dyed a bright reddish-yellow shade of goodfastness to washing and to light.

If the dyestutf used in the above example is replaced by the dyestuif ofExample 2, the yarn is dyed a reddishorange shade of good fastness toWashing and to light.

Example 7 100 parts of plain weave bleached cotton fabric are padded atroom temperature with an aqueous solution containing 1% of the dyestuifof Example 2, 2% sodium- Example 8 A printing paste is obtained bymixing together 5 parts of urea, 49 parts of water, 1 part of sodiumbicarbonate, 40 parts of 5% aqueous sodium alginate and 5 parts of thedyestulf of Example 1.

The printing paste so obtained is printed on to cotton fabric from aroller, and the fabric is then dried and steamed for 5 minutes. Thefabric is then rinsed in water, treated in boiling 0.2% aqueous soapsolution for 10 minutes, again rinsed inwater and dried.

A bright reddish-yellow print is obtained having very good fastness towashing and to light.

If the dyestuif used in the above printing paste is replaced by an equalweight of the dyestuif of Example 2, there is obtained a bright orangeprint having very good fastness to washing.

Example 9 A printing paste is obtained by mixing together 5 parts ofurea, 50 parts of water, 40 parts of 5% aqueous sodium alginate solutionand 5 parts of the dyestuif of Example 1.

This printing paste is applied to mercerised cotton fabric by rollermachine printing and the fabric is dried. The dried fabric is thenpassed through a padding mangle with the printed side of the fabricfacing the lower padding roller. This lower roller is partially immersedin an aqueous solution containing 2% of sodium bicarbonate and 0.4% ofsodium alginate. The padded fabric is then immediately passed over aseries of steam heated drying cylinders. The dried fabric is then rinsedin cold water, treated in boiling 0.2% aqueous soap solution for 5minutes, again rinsed in cold Water and dried. The bright reddish-yellowprint so obtained possesses very good fastness to washing and to light.

Example 10 A printing paste is obtained by mixing together 5 parts ofurea, 50 parts of water, 40 parts of 5% aqueous sodium alginate solutionand 5 parts of the dyestuff of Example 2.

This printing paste is applied to staple viscose rayon fabric by rollermachine printing and the fabric is dried. The dried fabric is thenpassed through a padding mangle with the printed side of the fabricfacing the lower padding roller. This lower roller is partially immersedin an aqueous solution containing 2% of sodium carbonate and 0.4% ofsodium alginate. The padded fabric is then immediately passed over aseries of steam heated drying cylinders. The dried fabric is then rinsedin cold water, treated in boiling 0.2% aqueous soap solution for 5minutes, again rinsed in cold water and dried. The bright orange printso obtained possesses very good fastness to washing and to light.

Example 11 The printing paste of Example 9 is applied to chlorinatedwool fabric by screen printing. The fabric is dried and steamed for 10minutes, rinsed in cold water, soaped for 5 minutes at 60 C. in asolution containing 2 parts of soap in 1,000 parts of water, rinsed anddried. The yellow print so obtained is fast to washing and to light.

1 Example 12 A printing paste is obtained by mixing together 10 parts ofurea, 25 parts of water, 60 parts of 8% aqueous Gum Tragacanth solutionand 5 parts of the dyestufi of Example 2.

This printing paste is applied to natural silk by screen printing. Thefabric is dried and then steamed for 10 minutes. The print is thenrinsed in cold water and soaped for 5 minutes at 50 C. in a solutioncontaining 2 parts of soap in 1,000 parts of water, rinsed and dried.The bright orange print so obtained is fast to washing and to light.

meme

11 1 Example 13 3 parts of the dyestufi of Example 2 are dissolved in4,000 parts of cold water. 4 parts of 85% formic acid and 100 parts ofnylon fabric are added. The dyestufi solution is heated to 95 C. anddyeing continued for 60 minutes. The fabric is then treated for minutesin 4,000 parts of liquor containing 4 parts of soap and 12 parts of sodaash. Finally the fabric is rinsed and dried. The nylon is dyed a brightorange shade.

Example 14 3 parts of the dyestuff of Example 2 are dissolved in 4,000parts of cold water and 100 parts of modified polyacrylonitrile fabricare added. The temperature is raised to 100 C. and 8 parts of sulphuricacid (specific gravity 1.8) are added slowly. Dyeing is continued for 60minutes after the last addition of sulphuric acid. The material is thentreated for 10 minutes at 85 C. in 4,000 parts of liquor containing 4parts of soap and 12 parts of soda ash. Finally the material is rinsedin cold water and dried. The fabric is dyed a bright orange shade.

Example 1 5 3 parts of the dyestuff of Example 1 are dissolved in 4,000parts of cold water. 100 parts of silk are added to the solution and 100parts of common salt are added gradually during 30 minutes. 8 parts ofsodium carbonate are then added during 15 minutes and dyeing iscontinued 'for a further 45 minutes. The silk is then treated with ahotaqueous solution containing 0.2% soap or synthetic detergent, 0.2%sodium carbonate and 0.5% common salt. The fabric is then rinsed anddried. The silk is then dyed to a yellow shade of good fastness towashing.

If the dyestuii used in the above example is replaced by the dyestufi ofExample 2 the silk is then dyed to a bright-orange shade of goodfastness to washing.

Example 16 A solution of 25.4 parts of the trisodium salt of l-amino-4(4' amino)anilinoanthraquinone 2:3':5 trisulphonic acid in a mixture of300 parts of water and 80 parts of ethanol is added during 15 minutes toa stirred, boiling solution of 7.7 parts of 2:4:6-trichloropyrimidine in100 parts of water and 240 parts of ethanol. The reaction mixture isstirred at the boil under a reflux condenser for 24 hours, during whichtime the acidity to litmus which develops is neutralised by the gradualaddition of 10% aqueous sodium carbonate solution. 80 parts of sodiumchloride are added, the mixture is stirred for a further 30 minutes atthe boil and then allowed to cool with stirring and stand for severalhours at roomtemperature. The dyestuit which separates is filtered,washed with a mixture (equal parts by vol.) of aqueous sodium chloridesolution and ethanol. The product is dissolved in 600 parts of water at55 C. and the solution screened and the dyestuff is reprecipitated bythe addition of sodium chloride at the rate of 1 lb. per gallon; whenseparation of the dyestulI' is complete, it is filtered, washed wellwith 10% aqueous sodium chloride solution and dried.

Example 17 11.07 parts of copper phthalocyanine 3-(N-3'-amino-4-sulphophenyl)sulphonamide sulphonic acid (obtained as described below)are dissolved in 500 parts of water at 70 C. and the pH of the solutionis adjusted to 7 by the addition of aqueous sodium hydroxide solution.10 parts of N/ 10 hydrochloric acid are added, followed by a solution of3.4 parts of 2:4:6-trichloropyrimidine in 50 parts of dioxan. Themixture is then refluxed for 7 hours, cooled to room temperature, andsuificient aque ous sodium hydroxide solution is added to bring the pHof the solution to 7. 175 parts of salt are added and the precipitateddyestufi is filtered off and dried.

The copper phthalocyanine 3-(N-3-amino-4-sulphophenyl) sulphonamidesulphonic acid used in the above example may be obtained as follows: 228parts of copper phthalocyanine is converted to the tetrasulphonchlorideby the method described in Example 1 of United Kingdom specification No.515,637 and the moist cake is suspended in 3000 parts of ice-water. 336parts of sodium bicarbonate are added, then a solution of 188 parts of2:4-diaminobenzene sulphonic acid in 1500 parts of water and 1000 partsof N aqueous sodium bicarbonate solution. The mixture is stirred for 18hours, during which time the temperature is allowed to rise to C.,

then the resulting blue solution is acidified by addition of 360 partsof38% aqueous hydrochloric acid. The mixture is filtered and the solidresidue is washed with 2 N aqueous hydrochloric acid and dried to give ablue powder.

What we claim is:

1. Water-soluble colored compounds selected from the group consisting ofazo, anthraquinone, phthalocyanine, and nitro-group-substitutedwater-soluble colored compounds substituted by a member selected fromthe group consisting of the 2:6-dihalogeno-4-primidylamino radical andthe 4:6-dihalogeno-2-pyrimidylamino radical.

2. Water-soluble azo colored compounds substituted by a substituentselected from the group consisting of the2:6-dihalogeno-4-pyiimidylamino radical and the4:6-dihalogeno-Z-pyrimidylamino radical.

3. Water-soluble anthraquinone colored compounds substituted by a memberselected from the group consisting of the2:6-dihalogeno-4-pyrimidylamino radical and the4:6dihalogeno-2-pyrirnidylamino radical.

4. Water-soluble colored phthalocyanine compounds substituted by amember selected from the group consisting of the2:6-dihalogeno-4-pyrimidylamino radical and the4:6-dihalogeno-2-pyrimidylamino radical.

5. Water-soluble nitro-group-substituted colored compounds substitutedby a member selected from the group consisting of the226-dihalogeno-4-pyrimidylamino radical and the4:6-dihalogeno-Z-pyrimidylamino radical.

6. 2-[2'-methyl 4' (dichloropyrimidylamino)-phenylazo] -naphthalene-48-disulfonic acid.

7. 2-(dichloropyrimidylamino) 6 (4-methylphenylazo -5 -naphthol-27-disulphonic acid.

8. 2 nitro 4 (dichloropyrimidylamino)diphenylamine-3z4-disulfonic acid.

9. 2-nitro-4'-N-methyl-N-(dichloropyrimidyl) amino- 4-sulph0n-betahydroxyethylamido diphenylamine 3- sulfonic acid.

10. 1-amino-4-(4 dichloropyrimidylamino) anilinoanthraquinone-Z 3 '-5-trisulfonic acid.

11. Copper phthalocyanine3-(N-3-dichloropyrimidylamino-4-sulfophenyl)sulfonamide sulfonic acid.

France Jan. 16, 1957 UNITED STATES PATENT OFFICE CERTIFICATION OFCORRECTION Patent No, 2 935506 May 3 1960 Robert Norman Heslop et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 12, line 28, for "primidylamino" read pyrimidylamino Signed andsealed this 29th day of August 1961.,

(SEAL) Attest:

ERNEST W. SWIDEQ v DAVID L. LADD Attest ing Officer I Commissioner ofPatents

1. WATER-SOLUBLE COLORED COMPOUNDS SELECTED FROM THE GROUP CONSISTING OFAZO, ANTHRAQUINONE, PHTHALOCYANINE, AND NITRO-GROUP-SUBSTITUTEDWATER-SOLUBLE COLORED COMPOUNDS SUBSTITUTED BY A MEMBER SELECTED FROMTHE GROUP CONSISTING OF THE 2:6-DIHALOGENO-4-PRIMIDYLAMINO RADICAL ANDTHE 4:6-DIHALOGENO-2-PYRIMIDYLAMINO RADICAL.